US9695201B2 - Process for preparing trialkyl compounds of metals of group IIIA - Google Patents

Process for preparing trialkyl compounds of metals of group IIIA Download PDF

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US9695201B2
US9695201B2 US14/358,069 US201214358069A US9695201B2 US 9695201 B2 US9695201 B2 US 9695201B2 US 201214358069 A US201214358069 A US 201214358069A US 9695201 B2 US9695201 B2 US 9695201B2
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reaction mixture
separator
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US20140287141A1 (en
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Ralf Karch
Andreas Rivas-Nass
Annika Frey
Tobias BURKERT
Eileen Woerner
Angelino Doppiu
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Umicore AG and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a process for the inexpensive and environmentally friendly preparation of trialkyl compounds of metals of group IIIA of the Periodic Table.
  • the compounds have the general formula R 3 M where M is a metal of group IIIA of the Periodic Table of the Elements (PTE), preferably gallium (Ga) or indium (In), and R is a C 1 -C 5 -alkyl group, preferably methyl or ethyl.
  • the process is based on the reaction of metal trichloride (MCl 3 ) with an alkylaluminium sesquichloride (R 3 Al 2 Cl 3 ) in the presence of at least one alkali metal halide as auxiliary base in a one-pot process.
  • the reaction mixture is heated to a defined temperature and the trialkylmetal compound is separated off from the reaction mixture via a separator, with partially alkylated products simultaneously being recirculated to the reaction mixture.
  • the present invention makes a more rapid process possible, in particular in the preparation of trimethylgallium.
  • the targeted use of inexpensive starting materials for example alkylaluminium sesquichloride
  • the yields are significantly improved.
  • trialkyl compounds of the type R 3 M preferably trimethylgallium, triethylgallium, trimethylindium and triethylindium, prepared according to the invention are suitable as precursors for metal organic chemical vapour deposition (MOCVD), a process which is widespread in, for example, the semiconductor and microelectronics industry.
  • MOCVD metal organic chemical vapour deposition
  • gallium alkyl compounds are prepared from gallium halide and trialkylaluminium as alkylating reagent are known.
  • Trialkylaluminium compounds are not toxic or light sensitive and are more thermally stable than corresponding mercury dialkyls or zinc dialkyls.
  • known processes usually proceed in two or more stages since starting materials or the product produced have to be purified or isolated in a complicated manner.
  • only small yields of gallium alkyl or indium alkyl compounds are frequently achieved by means of the known processes.
  • trimethylgallium is at present usually prepared from gallium trichloride and an excess of trimethylaluminium as methylating reagent.
  • the use of trimethylaluminium has the disadvantage that it has to be purified in a complicated manner before use as starting material, which makes the process for producing TMG expensive and time-consuming.
  • US 2006/0075959 A1 describes a process for preparing trimethylgallium using trimethylaluminium.
  • EP 1 489 085 A1 discloses the preparation of TMG by reaction of gallium trichloride with trimethylaluminium in organic solvents such as mesitylene or dichlorobenzene.
  • J. J. Eisch et al. describe a process for the preparation of triethylgallium and triisobutylgallium in hexane or pentane.
  • Potassium chloride is added in a virtually equimolar ratio to triethylaluminium or triisobutylaluminium in order to complex the dialkylaluminium, so that gallium chloride can be alkylated further.
  • the products are subsequently purified by redistillation over alkali metal fluorides in a further step (Eisch, J. J., J. Amer. Chem. Soc., 1962, 84, 3605-3610).
  • Gaines et al. refer to the preparation of trimethylgallium from trimethylaluminium and also a subsequent distillation over sodium fluoride followed by redistillation. The yield is only about 63% (Gaines, D. F., Borlin, J., Fody, E. P., in: Inorganic Syntheses, 1974, 15, 203-207).
  • DE 1158 977 describes the reaction of gallium trichloride with trialkylaluminium or trialkylaluminium etherate.
  • the trialkylgallium obtained is separated off by distillation and subsequently purified by rectification.
  • WO 00/37475 A1 discloses a continuous process for preparing TMG from trimethylaluminium and gallium trichloride in toluene.
  • EP13033366 too, describes a continuous process for preparing metal-organic compounds.
  • Starowieyski et al. describe the preparation of TMG from gallium trichloride and dimethylaluminium chloride in the presence of sodium chloride (Starowieyski K. B. et al, Applied Organometallic Chemistry, 2000, 14, 10, 616-622).
  • DE 40 05 726 A1 describes a process for preparing trialkylgallium compounds using alkylaluminium halides and in the presence of alkaline earth metal or alkali metal chlorides as auxiliary bases forming a salt melt at the reaction temperature.
  • DE 40 05 726 A1 refers to the use of alkylaluminium sesquichlorides (R 3 Al 2 Cl 3 ) for preparing gallium alkyl compounds. The process is carried out without recirculation (separator) of the partially alkylated products, and the yields of fully alkylated products are from 10 to 48% (direct yield).
  • the process should preferably be suitable for preparing trimethylgallium, triethylgallium, trimethylindium, and triethylindium. It should particularly preferably be suitable for preparing trimethylgallium and triethylgallium.
  • the process should be based on the use of industrially readily available starting materials and ensure high yields and a high efficiency in respect of the use of the expensive metal starting materials.
  • the object of the present invention is achieved by the subject matter according to the present claims.
  • the object is achieved by an improved process which is, inter alia, characterized by the starting substances used (e.g. alkylaluminium sesquichlorides) and the particular way of carrying out the reaction using a separator.
  • the present invention provides a process for preparing trialkylmetal compounds of the general formula R 3 M where
  • the process is based generally on the reaction of a metal trichloride (MCl 3 type) with an alkylating reagent.
  • MCl 3 type metal trichloride
  • the reaction takes place in a reactor which is advantageously operated batchwise.
  • a continuous process is also conceivable.
  • specific flow reactors and/or microreactors may be employed. Suitable reactor types and process-relevant modifications are known to the person skilled in the art.
  • the reaction preferably proceeds in an inert gas atmosphere (argon or nitrogen).
  • alkylaluminium sesquichlorides preferably methylaluminium sesquichloride (Me 3 Al 2 Cl 3 ) and ethylaluminium sesquichloride (Et 3 Al 2 Cl 3 ).
  • Me 3 Al 2 Cl 3 methylaluminium sesquichloride
  • Et 3 Al 2 Cl 3 ethylaluminium sesquichloride
  • These starting materials have the advantage that they are formed as intermediates in the preparation of trimethylaluminium or triethylaluminium and do not require complicated purification.
  • Such products are commercially available from various manufacturers (for example from Chemtura Organometallics GmbH, Bergkamen, DE).
  • the use of these alkylating reagents thus makes a more inexpensive and resource-sparing preparation possible compared to the conventional use of trimethylaluminium as starting material. It has surprisingly been found that, for example when using methylaluminium sesquichloride as methylating reagent in the process of the invention, high
  • trialkylmetal compounds preference is given to using from 1 to 10 equivalents of alkylaluminium sesquichloride per equivalent of metal trichloride. Further preference is given to using from 1 to 4 equivalents and particularly preferably from 1 to 2 equivalents of alkylaluminium sesquichloride per equivalent of metal trichloride. In a particularly preferred embodiment, 3 equivalents of alkylaluminium sesquichloride are used per equivalent of metal trichloride. In this way, particularly high yields of trialkylmetal compounds can be achieved.
  • the term “equivalent” as used in the present patent application refers to the molar ratios based on the molar amounts of the starting materials.
  • the reaction takes place in the presence of at least one auxiliary base.
  • the auxiliary base comprises at least one alkali metal halide, preferably at least one alkali metal chloride. Further preference is given to the alkali metal chlorides sodium chloride (NaCl) and potassium chloride (KCl) and mixtures thereof since these salts together with the Al-containing reaction products, in particular AlCl 3 , form a salt melt which is liquid at the reaction temperature. The use of additional organic solvents can therefore be dispensed with.
  • the alkali metal chloride is preferably water-free.
  • water-free means a water content of ⁇ 10 ppm, more preferably ⁇ 8 ppm and particularly preferably ⁇ 5 ppm.
  • a water content of >10 ppm can lead to secondary reactions and reduce the yield of trialkylmetal compound.
  • the auxiliary base particularly preferably comprises a mixture of potassium chloride and sodium chloride in which the molar ratio of sodium chloride to potassium chloride is in the range from 6:4 to 8:2, more preferably from 6:3 to 8:3 and particularly preferably from 6.5:3 to 7.5:3. Adherence to such a molar ratio surprisingly leads to particularly high yields of TMG despite the high proportion of sodium. In a particularly preferred embodiment, the molar ratio of sodium chloride to potassium chloride is 7:3.
  • the ratio of equivalents of the sum of sodium chloride and potassium chloride used to the number of equivalents of the alkylating reagent used is preferably from 1.5:1 to 2.5:1, more preferably from 1.75:1 to 2.25:1. In a particularly preferred embodiment, the ratio of the equivalents of the sum of sodium chloride and potassium chloride used to the number of equivalents of the methylating reagent used is 2:1. This makes it possible to prepare the trialkylmetal compounds in a particularly high yield.
  • the introduction of the starting materials for example gallium trichloride and methylaluminium sesquichloride (Me 3 Al 2 Cl 3 ), into the reactor is preferably time offset.
  • the starting materials for example gallium trichloride and methylaluminium sesquichloride (Me 3 Al 2 Cl 3 )
  • the auxiliary base and the metal halide can simply be weighed into the reactor.
  • Auxiliary base and gallium halide are preferably present in the solid state. Controlled addition of the liquid alkylating reagent can subsequently be carried out.
  • the addition of the alkylating reagent to the mixture of metal trichloride and auxiliary base is generally carried out via a dropping funnel.
  • the addition of the alkylating reagent is preferably carried out with stirring of the mixture of metal halide and auxiliary base in order to ensure satisfactory mixing and quantitative conversion.
  • the temperature during the addition of the alkylating reagent is preferably below 130° C. Particular preference is given to a temperature of 130° C. not being exceeded during the addition of the alkylating reagent in order to avoid undesirable secondary reactions. Since the reaction is strongly exothermic, it is preferably controlled via the speed of addition and the partial amounts of the alkylating reagent which are added in each case.
  • a mixture comprising metal trichloride and auxiliary base is initially charged and alkylaluminium sesquichloride (R 3 Al 2 Cl 3 ) is subsequently added to this mixture with a time offset in step a).
  • a mixture comprising alkylaluminium sesquichloride (R 3 Al 2 Cl 3 ) and auxiliary base is initially charged and metal trichloride is subsequently added to this mixture with a time offset in step a).
  • the reaction mixture After the reaction of the metal chloride with the alkylating reagent, the reaction mixture is heated to a temperature above 120° C., preferably above 130° C., and the trialkylmetal compound (R 3 M) is separated off from the reaction mixture.
  • This separation is not quantitative; it preferably serves to remove the reaction product from the reaction mixture and thus shift the equilibrium in the direction of the reaction products.
  • R 3 M trialkylmetal compound
  • This separation is not quantitative; it preferably serves to recirculate the partially alkylated products to the reaction mixture in order to complete alkylation.
  • the removal of the reaction product (trialkylmetal compound R 3 M) from the reaction mixture shifts the equilibrium in the direction of the reaction products.
  • the process of the invention differs from the process previously disclosed in DE 40 05 726 in a modified way of carrying out the reaction and in particular in the use of a “separator”.
  • the use of this separator according to the invention surprisingly enables the desired trialkylgallium compound to be obtained in a significantly higher direct yield under comparable reaction conditions.
  • reaction equation (1) indicates the way in which the reaction proceeds only imprecisely and incompletely.
  • direct transfer of all methyl groups from aluminium to gallium cannot be observed, but instead only a partial alkylation in which dimethyl gallium chloride (Me 2 GaCl) is formed;
  • equation (2) initially takes place at temperatures below 120° C.: GaCl 3 +Me 3 Al 2 Cl 3 +2Na/KCl ⁇ Me 2 GaCl+Na/KMeAlCl 3 +Na/KAlCl 4 (2)
  • the second alkylation step does not take place and only Me 2 GaCl can be isolated as product immediately after the addition of GaCl 3 to the Me 3 Al 2 Cl 3 .
  • reaction can be carried out in a 4-neck flask provided with stirrer, dropping funnel, a separator and a further outlet.
  • Corresponding pilot plants can, for example, be constructed in stainless steel.
  • the trialkylmetal compound (R 3 M) formed in reaction step a) is isolated from the residual mixture remaining in the reactor.
  • the isolation is preferably carried out by distillation using a separator which in principle represents a heated separation element.
  • a separator which in principle represents a heated separation element.
  • a heated packed column or a heated reflux condenser can be used on the laboratory scale.
  • appropriately dimensioned industrial embodiments should be used.
  • the separator is generally operated at atmospheric pressure (1 ⁇ 0.2 bar) and heated to a temperature which is from 5 to 40° C. above, preferably from 10 to 25° C. above, the boiling point of the trialkylmetal compound R 3 M formed in the reaction mixture.
  • the separator is heated to a temperature in the range from 60 to 90° C., preferably to a temperature in the range from 70 to 80° C. It is particularly preferably operated at about 70° C. This temperature is 14° C. above the boiling point of TMG and 98° C. below the boiling point of dimethylgallium chloride (b.p. 168° C.).
  • the isolation by distillation via the separator is preferably carried out under atmospheric pressure.
  • the separator is heated to a temperature in the range from 150 to 180° C., preferably to a temperature in the range from 155 to 170° C. when carrying out the process at atmospheric pressure (1 ⁇ 0.2 bar).
  • the process of the invention is preferably carried out under reduced pressure in step b) and the temperature of the separator is adapted to the reduced boiling point of the partially alkylated product.
  • the boiling point of diethylgallium chloride is 60-62° C. (at 3 mbar).
  • a separator temperature in the range from 100 to 160° C., preferably in the range from 120 to 150° C., at a reduced pressure in the range to 1 mbar (10 ⁇ 3 bar) has been found to be useful in the process of the invention.
  • the reaction mixture is in step c), heated further to a temperature in the range from 165° C. to 350° C., preferably to a temperature in the range from 180° C. to 300° C.
  • the remaining trialkylmetal compound (R 3 M) and the partially alkylated products (MCl x R y ) are separated off from the reaction mixture.
  • This isolation is preferably carried out by distillation with application of a reduced pressure. Preference is given to selecting a fine to high vacuum in the range from 10 ⁇ 1 to 10 ⁇ 4 mbar. The reduced pressure makes it possible to use comparatively low temperatures, so that an inexpensive process is possible.
  • the isolation of the residue is preferably effected via a separate outlet on the reactor.
  • the trialkylmetal compounds (R 3 M) and the partially alkylated products (MCl x R y ) isolated by the separation in step c) are re-used in a subsequent batch and added to the fresh reaction mixture (cf. step d) of the process of the invention).
  • step d) If an excess of alkylating reagent ( ⁇ 3 equivalents of alkylaluminium sesquichloride) is employed, reuse as per step d) can be dispensed with and the reaction product from step c) can be passed directly to fine purification.
  • This optional recycling of the expensive metal compounds makes the process of the invention particularly economical.
  • the gallium utilization and the TMG yield can be increased further.
  • a salt melt which is liquid at the reaction temperature preferably remains as residual mixture after carrying out steps a) to c).
  • no pyrophoric alkyl metal compounds remain in the residual mixture.
  • the residual mixture particularly preferably comprises compounds selected from among Na/K[AlCl 4 ], Na/K[MeAlCl 3 ] and mixtures thereof.
  • direct yields in the range from 60 to 90% can surprisingly be achieved by means of the process of the invention.
  • the direct yield or “crude yield” is the yield after step b) of the process.
  • the trialkylmetal compounds obtained in the direct yield generally still contain from 0.1 to 1% by weight of the dimethylated products (measured by means of 1 H-NMR).
  • the heating step c) is optional and may be dispensed with.
  • the direct yield or “crude yield” of trialkyl metal compound after step b) is obtained.
  • the trialkylmetal compounds obtained in steps b) and optionally c) of the process are generally subjected to a fine purification in a subsequent step. This is generally a rectification and/or a distillation, optionally in a plurality of steps. Highly pure trialkylmetal compounds which meet the requirements of the MOCVD industry are obtained in this way
  • trialkylmetal compounds in particular trimethylgallium (TMG) or triethylgallium (TEG), prepared by the process of the invention are particularly suitable as metal organic precursor for metal organic chemical vapour deposition (MOCVD), for example for producing semiconductor layers composed of GaAs.
  • MOCVD metal organic chemical vapour deposition
  • semiconductor layers III/V semiconductors, etc. ultimately produced therefrom have a variety of industrial uses.
  • the products and the sesquichlorides used in the synthesis are pyrophoric. All work is therefore carried out with rigorous exclusion of air and moisture under protective gas (argon, nitrogen).
  • TMG Trimethylgallium
  • Me 3 Ga can be isolated above 155° C.
  • the reaction temperature reaches 180° C.
  • isolation of the product via the separator is stopped. This gives a total of 89.0 g of Me 3 Ga (corresponding to a direct yield of 68%).
  • the Me 3 Ga present in the direct yield contains 0.5% by weight of Me 2 GaCl (measured by means of 1 H-NMR).
  • a reduced pressure (to 10 ⁇ 3 mbar, oil pump) is applied and the remaining Ga-containing compounds (47 g, mixture of Me 3 Ga and Me 2 GaCl) are removed from the reaction mixture via a second outlet.
  • the total yield is 72.2% of Me 3 Ga. Taking into account 27.4% of Me 2 GaCl, the total conversion based on Ga is thus 99.6%.
  • the Me 3 Ga present in the direct yield contains 0.5% by weight of Me 2 GaCl (measured by means of 1 H-NMR).
  • the mixture of Me 3 Ga and Me 2 GaCl is reused in other batches (cf. Example 2).
  • the isolation of the product via the separator is stopped and the remaining Ga-containing compounds (residue) are isolated from the residual mixture via the second outlet with application of a reduced pressure (70.0 g, mixture of Me 3 Ga and Me 2 GaCl).
  • the total yield is 64.0% of Me 3 Ga. Taking into account 35.8% of Me 2 GaCl, the total conversion (based on Ga) is 99.8%.
  • the isolated crude Me 3 Ga from the direct yield contains 0.8% by weight of Me 2 GaCl (measured by means of 1 H-NMR).
  • the mixture of Me 3 Ga and Me 2 GaCl is recirculated as starting material instead of GaCl 3 in a further pass.
  • the isolation of the product via the separator is stopped and the remaining Ga-containing compounds are removed from the residual mixture via a second outlet with application of a reduced pressure (6.9 g).
  • a reduced pressure (6.9 g).
  • 99.0% of Me 3 Ga and 0.9% of Me 2 GaCl are isolated, and the total conversion (based on Ga) is 99.9%.
  • the isolated crude TMG contains 0.7% by weight of Me 2 GaCl and 1.4% by weight of Me 2 AlCl (measured by means of 1 H-NMR).
  • Et 3 Ga In total, 80.9% of Et 3 Ga and 19% of Et 2 GaCl are isolated, and the total yield (based on Ga) is 99.9%.
  • the isolated crude Et 3 Ga contains 2.6% by weight of Et 2 GaCl (measured by means of 1 H-NMR).
  • Example 6 The experimental conditions are identical to Example 6, but the experiment is carried out without use of a separator.
  • a 500 ml 4-neck flask equipped with stirrer, thermocouple and dropping funnel is charged with GaCl 3 (50.0 g, 0.28 mol) and methylaluminum sesquichloride (58.3 g, 0.28 mol, 1 equivalent) is added dropwise via the dropping funnel.
  • the flask is transferred to a glovebox and dry NaCl (23.2 g, 0.40 mol, 1.4 equivalents) and dry KCl (12.7 g, 0.17 mol, 0.6 equivalent) are added.
  • the dropping funnel is replaced with a CLAISEN head with attached cold-trap.
  • the apparatus is taken out of the glovebox and the reaction mixture is slowly heated under constant stirring to 350° C. At a temperature between 100 and 120° C.
  • reaction mixture becomes liquid; between 155 and 160° C. a clear liquid starts to distill off and is collected in an ice-cooled cold-trap.
  • the collected product at room temperature partially solid, overall 36.9 g, is identified by means of NMR as a mixture of Me 3 Ga and Me 2 GaCl, containing 21.3% Me 3 Ga and 78.7% Me 2 GaCl.
  • a 250 ml 4-neck flask equipped with stirrer, thermocouple, dropping funnel and separator with an attached cold-trap is charged in a glovebox with InCl 3 (10.0 g, 45.2 mmol), dry NaCl (3.67 g, 63.3 mmol, 1.40 equivalents) and dry KCl (2.02 g, 27.1 mmol, 0.6 equivalents) and the dropping funnel is charged with methylaluminum sesquichloride (9.29 g, 45.2 mmol, 1.0 equivalent).
  • the apparatus is transferred out of the glovebox and methylaluminum sesquichloride is added to the salt mixture.
  • the reaction mixture is then slowly heated to 150° C. under constant stirring with the temperature of the separator set to 80° C.
  • the cold-trap When the reaction mixture is completely liquid, the cold-trap is cooled with liquid nitrogen and by applying a vacuum (10 ⁇ 3 mbar) to the apparatus, trimethylindium is sublimed into the cold-trap. When all trimethylindium is sublimed out of the reaction flask the product isolation via the separator is stopped, a new cold-trap is attached directly to the reaction flask and the remaining dimethylindium chloride in the reaction mixture is sublimed out by raising the temperature up to 250° C.

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US14/358,069 2011-11-28 2012-11-28 Process for preparing trialkyl compounds of metals of group IIIA Active US9695201B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE102011119487 2011-11-28
DE102011119487.1 2011-11-28
DE102011119487 2011-11-28
DE201210013941 DE102012013941A1 (de) 2012-07-16 2012-07-16 Verfahren zur Herstellung von Galliumtrialkylverbindungen
DE102012013941 2012-07-16
DE102012013941.1 2012-07-16
PCT/EP2012/073771 WO2013083449A1 (en) 2011-11-28 2012-11-28 Process for preparing trialkyl compounds of metals of group iiia

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TWI632149B (zh) * 2011-11-28 2018-08-11 烏明克股份有限兩合公司 第iii a族金屬的三烷基化合物之製法
US8513447B1 (en) * 2012-02-01 2013-08-20 Chemtura Corporation Preparation of tri-alkyl gallium or tri-alkyl indium compounds
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EP3704128B1 (en) * 2017-10-31 2022-09-28 Nouryon Chemicals International B.V. Method for storing and/or transporting gallium chloride
WO2019115377A1 (en) * 2017-12-13 2019-06-20 Akzo Nobel Chemicals International B.V. Process for purification of dimethyl aluminium chloride

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1158977B (de) 1960-05-14 1963-12-12 Siemens Ag Verfahren zur Herstellung von Galliumtrialkylen
DE4005726A1 (de) 1989-04-28 1990-10-31 Messer Griesheim Gmbh Verfahren zur herstellung von galliumalkylverbindungen
US5043462A (en) * 1989-04-28 1991-08-27 Messer Greisheim Process for the production of gallium-alkyl compounds
US5350869A (en) 1993-07-27 1994-09-27 Cvd, Incorporated Purification of trialkylgallium, synthesis of trialkylgallium
US5473090A (en) 1992-07-02 1995-12-05 Air Products And Chemicals, Inc. Process for the preparation of trialkyl compounds of group 3a metals
US5756786A (en) 1997-06-25 1998-05-26 Morton International, Inc. High purity trimethylindium, method of synthesis
JP2000005503A (ja) 1998-06-24 2000-01-11 Nippon Shokubai Co Ltd 反応蒸留装置および反応蒸留方法
WO2000037475A1 (en) 1998-12-19 2000-06-29 Epichem Limited Process and apparatus for production of organometallic compounds
WO2002007848A1 (en) 2000-07-22 2002-01-31 Epichem Limited Process and apparatus for the isolation of pure, or substantially pure, organometallic compounds
US20020188145A1 (en) * 2001-04-06 2002-12-12 Shipley Company, L.L.C. Trialkyl Group VA metal compounds
US20030191333A1 (en) 2002-04-06 2003-10-09 Shipley Company, L.L.C. Trialkylindium preparation
EP1489085A1 (en) 2003-06-19 2004-12-22 Shin-Etsu Chemical Co., Ltd. Preparation of high purity alkyl gallium
US20060047132A1 (en) 2004-09-02 2006-03-02 Rohm And Haas Electronic Materials Llc Method
US20060075959A1 (en) 2004-10-13 2006-04-13 Sumitomo Chemical Company, Limited Trimethylgallium, a method for producing the same and a gallium nitride thin film grown from the trimethylgallium
EP1705719A1 (en) 2005-03-23 2006-09-27 Nichia Corporation Methods for producing trialkyl gallium
JP2006265168A (ja) 2005-03-23 2006-10-05 Nichia Chem Ind Ltd トリアルキルガリウムの製造方法
CN1872861A (zh) 2005-06-03 2006-12-06 大连保税区科利德化工科技开发有限公司 三甲基镓生产方法及设备
CN1872862A (zh) 2005-06-03 2006-12-06 大连保税区科利德化工科技开发有限公司 三甲基镓制备和提纯方法
JP2006342101A (ja) 2005-06-09 2006-12-21 Shin Etsu Chem Co Ltd 有機金属化合物の製造方法
US20090054717A1 (en) 2007-08-21 2009-02-26 The Nippon Synthetic Chemical Industry Co., Ltd. Method of Producing 3,4-Diacyloxy-1-Butene
JP2009126835A (ja) 2007-11-27 2009-06-11 Ube Ind Ltd 高純度トリアルキルガリウム及びその製法
US20090149008A1 (en) 2007-10-05 2009-06-11 Applied Materials, Inc. Method for depositing group iii/v compounds
JP2010195690A (ja) 2009-02-23 2010-09-09 Ube Ind Ltd 高純度トリアルキルガリウム及びその製造方法
WO2013083449A1 (en) 2011-11-28 2013-06-13 Umicore Ag & Co. Kg Process for preparing trialkyl compounds of metals of group iiia

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009007786A (ja) * 2007-06-26 2009-01-15 Miracle Three Corporation 階段室型共同住宅の増築方法及びこの方法で増築された建築物

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1158977B (de) 1960-05-14 1963-12-12 Siemens Ag Verfahren zur Herstellung von Galliumtrialkylen
US3318931A (en) 1960-05-14 1967-05-09 Siemens Schukertwerke Ag Method of producing alkylgalliums
DE4005726A1 (de) 1989-04-28 1990-10-31 Messer Griesheim Gmbh Verfahren zur herstellung von galliumalkylverbindungen
JPH02295991A (ja) 1989-04-28 1990-12-06 Messer Griesheim Gmbh ガリウムアルキル化合物の製法
US5043462A (en) * 1989-04-28 1991-08-27 Messer Greisheim Process for the production of gallium-alkyl compounds
US5473090A (en) 1992-07-02 1995-12-05 Air Products And Chemicals, Inc. Process for the preparation of trialkyl compounds of group 3a metals
JPH08501532A (ja) 1992-07-02 1996-02-20 エア プロダクツ アンド ケミカルズ インク ３ａ族金属のトリアルキル化合物の製法
US5350869A (en) 1993-07-27 1994-09-27 Cvd, Incorporated Purification of trialkylgallium, synthesis of trialkylgallium
US5756786A (en) 1997-06-25 1998-05-26 Morton International, Inc. High purity trimethylindium, method of synthesis
JP2000005503A (ja) 1998-06-24 2000-01-11 Nippon Shokubai Co Ltd 反応蒸留装置および反応蒸留方法
WO2000037475A1 (en) 1998-12-19 2000-06-29 Epichem Limited Process and apparatus for production of organometallic compounds
JP2002533348A (ja) 1998-12-19 2002-10-08 エピケム リミテッド 有機金属化合物の製造のための改良された方法および装置
US6495707B1 (en) 1998-12-19 2002-12-17 Epichem Limited Process and apparatus for production of organometallic compounds
WO2002007848A1 (en) 2000-07-22 2002-01-31 Epichem Limited Process and apparatus for the isolation of pure, or substantially pure, organometallic compounds
EP1303336A1 (en) 2000-07-22 2003-04-23 Epichem Limited Process and apparatus for the isolation of pure, or substantially pure, organometallic compounds
US20020188145A1 (en) * 2001-04-06 2002-12-12 Shipley Company, L.L.C. Trialkyl Group VA metal compounds
US20030191333A1 (en) 2002-04-06 2003-10-09 Shipley Company, L.L.C. Trialkylindium preparation
EP1489085A1 (en) 2003-06-19 2004-12-22 Shin-Etsu Chemical Co., Ltd. Preparation of high purity alkyl gallium
US20060047132A1 (en) 2004-09-02 2006-03-02 Rohm And Haas Electronic Materials Llc Method
EP1643547A1 (en) 2004-09-02 2006-04-05 Rohm and Haas Electronic Materials, L.L.C. Preparation of group 12 and 13 metal compounds having low levels of oxygenated impurities
JP2006104189A (ja) 2004-09-02 2006-04-20 Rohm & Haas Electronic Materials Llc 有機金属化合物および有機金属化合物を製造する方法
US7166734B2 (en) 2004-09-02 2007-01-23 Rohm And Haas Electronic Materials Llc Method for making organometallic compounds
US20060075959A1 (en) 2004-10-13 2006-04-13 Sumitomo Chemical Company, Limited Trimethylgallium, a method for producing the same and a gallium nitride thin film grown from the trimethylgallium
EP1705719A1 (en) 2005-03-23 2006-09-27 Nichia Corporation Methods for producing trialkyl gallium
JP2006265168A (ja) 2005-03-23 2006-10-05 Nichia Chem Ind Ltd トリアルキルガリウムの製造方法
CN1872862A (zh) 2005-06-03 2006-12-06 大连保税区科利德化工科技开发有限公司 三甲基镓制备和提纯方法
CN1872861A (zh) 2005-06-03 2006-12-06 大连保税区科利德化工科技开发有限公司 三甲基镓生产方法及设备
JP2006342101A (ja) 2005-06-09 2006-12-21 Shin Etsu Chem Co Ltd 有機金属化合物の製造方法
US20090054717A1 (en) 2007-08-21 2009-02-26 The Nippon Synthetic Chemical Industry Co., Ltd. Method of Producing 3,4-Diacyloxy-1-Butene
JP2009067786A (ja) 2007-08-21 2009-04-02 Nippon Synthetic Chem Ind Co Ltd:The ３，４−ジアシロキシ−１−ブテンの製造方法
US20090149008A1 (en) 2007-10-05 2009-06-11 Applied Materials, Inc. Method for depositing group iii/v compounds
JP2009126835A (ja) 2007-11-27 2009-06-11 Ube Ind Ltd 高純度トリアルキルガリウム及びその製法
JP2010195690A (ja) 2009-02-23 2010-09-09 Ube Ind Ltd 高純度トリアルキルガリウム及びその製造方法
WO2013083449A1 (en) 2011-11-28 2013-06-13 Umicore Ag & Co. Kg Process for preparing trialkyl compounds of metals of group iiia
US20140256974A1 (en) 2011-11-28 2014-09-11 Umicore Ag & Co. Kg Process for preparing trialkylgallium compounds

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
C. A. Kraus et al., "Trimethyl Gallium, Trimethyl Gallium Etherate and Trimethyl Gallium Ammine"; Chemistry: Kraus and Toonder, Proc. N. A. S.; 1933; pp. 292-298.
D. F. Foster et al., "Electronic Grade Alkyls of Group 12 and 13 Elements"; Inorganic Syntheses, vol. 31, 1997, pp. 29-66.
Gaines et al., "Trimethylgallium", Inorganic Syntheses, pp. 203-207.
International Preliminary Report on Patentability for PCT/EP2012/073771 dated Jun. 3, 2014 (5 pages).
International Search Report for PCT/EP2012/073771; mailed Mar. 25, 2013.
J.J. Eisch et al, "Organometailic Compounds of Group III. I. The Preparation of Gallium and Indium Alkyls form Organoaluminum Compounds18", vol. 84, No. 19, pp. 3605-3610, Oct. 17, 1962.
L. I. Zakharkin et al., "A Simple Synthesis of Non-Solvated Trimethylgallium and Triethylgammium"; Synth. React. Inorg. Met.-Org., and Nano-Met. Chem, vol. 29 (7); (1999) 1243-1247.
Notification of Reasons for Refusal in JP 2014-542885 dated May 23, 2016 in Japanese with English Machine Translation (9 pages).
Notification of Transmittal of the International Search Report and the Written Opinion for Application No. PCT/EP2012/073772 mailed Mar. 25, 2013.
Search Report by Registered Searching Organization in JP 2014-542885 dated May 18, 2016 in Japanese with English machine translation (39 pages).
Starowieyski et al., "Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)44 (Me3Ga)", Applied Organometallic Chemistry, vol. 14, pp. 616-622, 2000.

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